Medium for bleaching, cracking, and desulphurizing petroleum and other hydrocarbon compounds and process of preparing same



Patented Get; 27, 1925.

UNITED STATES 1,558,631 PATENT oFFicE.

HERMAN BEINBOLD AND HUGO BEINIBOLD, OF OMAHA, NEBRASKA; SAID HUGO REINBOLD .ASSIGNOR' '10 SAID HERMAN MEDIUNZ FOB BLEACHING, CRACKING, AND DESULPHURIZING PETROLEUM AND OTHER HYDBOGAR BON COMPOUNDS AND PROCESS OF PREPARING BAKE.

No Drawing. Original application filed January 21, 1824, Serial No. 687,654. Divided and thil applicatlon filed May 19, 1924; Serial No. 714,470. a

To all whom it may concern:

Be it known that we, HERMAN REINBOLD v and HUoo REINBOLD, citizens of the United States of America, residing at Omaha, in

6 the county of Douglas and State of Nebraska, have invented certain new and useful improvements in mediums for bleaching, cracking, and desulphurizing petroleum and other hydrocarbon compounds and 10 processes of preparing same, of which the following is a specification.

This invention relates to the use of. clay,-

especially a colloid clay of the bentonite type, as a medium for refining and distilling I oils and to the processes of preparing and using the same.

The use of. anhydrous aluminum chloride has been practised in the refining of petroleum and other oils. The high cost and limited supply thereof, has, however, made its general use impractical.

The objects of the present invention are:

To provide a source of supply for the aluminum chloride;

To provide a highly porous, active substance or base in which the aluminum chloride is held in colloidal dispersion so as to present a maximum active surface for reaction on' the hydro-carbons;

To provide in addition tothe porous base and aluminum chloride an additional catalyst which will raise the volatizing temperature'of the aluminum chloride so that oils, such as shale oils and high asphalt content oils, which are volatile only at temperatures above that of aluminum chloride may be treated;

To provide a porous colloidal base for either or both the aluminum chloride and 40 the additional catalyst which will in itself j be an active agent in the oil refining process.

Other objects and advantages will become apparent in the preparation of the product and in its use as an oil treating l5 medium and itis desired to be understood that all such objects and advantages are anticipated and within the spirit of this invention.

The invention will be described as per-. taining to bentonite but it 1s, of course,

not limited only to bentonite, it bein equally applicable to all colloidal orplastic alumina-silicates, or any other clays which are chemically co'mplex alumino-silicates altered by lnfiltration or other causes, due to the geological conditions under which they were formed. The rocess is also applicable to all solid alumino-silicates which can be converted into the hydrous variety by chemical treatment.

Our new oil treating compound or medium is prepared for use by the following ste s.

Er) Grinding. The clay varying from 4 to 7 mesh.

(b) Wetting. The ground bentonite is soaked in water suf'ficient only to penetrate all of the res of the mineral without forming a ell Bentonite (as explained in our co-pen ing application, Serial No. 669,306, filed Oct. 18, 1923) is a very collo1da l clay and has the pro erty of swelling to a elly-like mass of great y increased volume upon the addition of water. Therefore, in this step care must be taken to add only enough water to fill the pores without causing it to jelly and destroy its original structure and shape. 1 The water is added for the purpose of reducing the concentration of the hydrochloric acid and preventing the destruction is ground to size of the structure of the clay by too rapid tated. Because of the greater solubility of the hydrochloric acid at a low temperature this step is carried on at ordinary room temperature. The mixture is now allowed to stand for from 10 to 12 hours. Bentonite is an hydrated aluminum-silicate containing in its natural state from 20 to 25 per cent alumina, some infiltrated impurities such as lime, magnesia, iron, etc., and a small percentage of alkalies. -These impurities and alkalies have no harmful effect on the compound, however. In this step, aluminum chloride Anon is 'formed by the aluminum of the bentonite and the chlorine of the hydrochloric acid, and hydrous silicic acid or silica gel is formed by the splitting of the silica from the bentonite or aluminum silicate. v During the setting period the aluminum chloride is adsorbed by the silica gel and held in colloidal and molecular dispersion retaining the original bentonite structure. v

In this highly dispersed and highly active condition it presents a maximum surface to the oils being treated.

Should the compound be intended for use on shale oils or other oils or .fractionations having a high boiling point, lithium carbonate (or chloride) is gradually added to the mixture after the addition of the hydrochloric acid.

The lithium base forms, in combination with the hydrochloric acid, lithium chloride (LiCl) which is volatile only at temperatures above 600 C. while aluminum chloride, under ordinary conditions, volatilizes at about 183 C. The lithium chloride, however, has further benefical properties on the compound in that We have found it to be an excellent catalyst, even more active than the aluminum chloride, either alone or in the mixture described, and it, therefore, greatly assists the action of the colloid compound. As little as 2 per cent lithium chloride has been found to be effectual in raising the volatilizing point of the aluminum chloride. Hydrogen chloride gas can, of course, be substituted in this step for the solution of hydrochloric acid.

(d) De-watering. The mixture is very gradually and carefully heated to a temperature of approximately 300 C. The heating should be continued until all of the mechanically contained water has been driven off and all except from 3 to 5 per cent of the water of constitution has been removed from the hydrous silicic acid. Further heating would result in driving out the hydrochloric acid and forming inactive aluminum silicate and in breaking down the structure of, and deactivating the silica gel. It is therefore absolutely essential that a small percentage of the Water of constitution remain in the compound.

If the above described process has been carried out successfully, the resulting product is a highly porous, colloidal substance which consists of a loosely chemically-combined, or colloidally and molecularly dis persed, aluminum chloride with a hydrous silicious acid in the form of a solid gel. No aluminum chloride has been volatilized and neutral and only slightly soluble.

When the above prepared compound, in granular or pulverized form, is mixed with crude petroleum or its "'fractionations, in the liquid hase, and then boiled and distilled, or if t ev oil is passed in the vapor phase through the compound, it will, like anhydrous aluminum chloride, not only crack or transform' the unsaturated hydro-carbons into saturated hydro-carbons, but willfaccording to the constitution of the crude oil and the temperature at which it is distilled,

decom ose the heavier hydro-carbons into the lig ter hydro-carbons and at the same time will decolorize and desulphurize the product.

The most effective method of treatin the oils with the improved treatin me 'ium has been found to pass the hydro-carbon vapors through a bed of the compound at the proper temperature for the fractiona-' tions desired and at atmospheric pressure.

The above noted results in the use of the compound on the crude oils appear to be not only due to the well known action of the aluminum chloride but also to the action of the hydrous silicic acid, which is loosely combined with the aluminum chloride. The hydrous silicic acid acts as a catalyst and assists the action of the aluminum chloride and the lithium chloride and since it has great adsorption properties for vapors and gases, it probably acts as a contillct si bstance releasing the sulphur from t e oi The action of the lithium chloride in raising the volatilizing-temperature of the Among many others we isolated at leastthree distinct" Al:Li chlorides, which represent true molecular combinations. Many tests and experiments proved the temperatures of separation and dissociation A1 and Li of the three, to be approximately 360, 420 and 550 degrees C. allowin for a varition of ten degrees on account 0 the melting point being close to dissociation temperature. Only slight fuming is observed, proving that only very little aluminum chloride is lostover its own volatilization temperature' of 183 degrees. At the points of dissociation of the AlzLi combination the aluminum. chloride is expelled as copious fumes.

This behavior accounts for the superiority of the aluminum-lithium catalyst over A1201 alone, both as to mixtures of hydrocarbons of difierent specific gravity and constitution and at different temperatures when used as a cracking medium. Whether the action is urely chemical, a contact substance, or ue to ionization we have not yet been able to determine. Lithium, having an atomic weight of 6.94 and an isotope 'forms only a small percentage of the active catalyst in combination with aluminum Having thus described the invention what 35 chloride and its cost offers no objection for its technical use.

The extreme afiinity of aluminum and lithium is evidenced b the fact, that the ores. and minerals use in our large scale production are spodumene (Al-Li trisilicate) and amblygonite (Al-Li phosphate).

While we have described in some detail a preferred method of preparing .our medium and of carrying out our process, together with the theories which we believe best explain the success of the process, it is understood that our invention is not limited.

to the precise procedure described nor is it dependent upon the accurac of the theories which We have advanced. n the contrary, our invention is not to be regarded as limit ed exce t in so far as such limitations are include within the terms of the accompanying claims, in which it is our intention to claim all novelty inherent in our invention as. broadly as is permissible" in view of'the prior art.

This invention was originally claimed in an application for Letters Patent on improvements in mediums for bleaching cracking and desulphurizing etroleum an other hydro-carbon compoun s and process of preparing same, filed by us J anuary 21, 1924, bearing Serial No. 687,654. This apglication and copending application, Serial umber 714,471, are divisions of the former application. v

we claim and desire secured by Letters Patent is: 7 I

1. The use of a lithium base material treated with hydrochloric acid as an oil treating medium.

2. An oil treating medium comprisinghydrous silicic acid in combination with lithium chloride.

3. The use of lithium chloride in an oil treating medium. I

4. The use of lithium chloride as a catalyst in preparin a medium for the refining and distilling 0 oils.

5. The use of a lithium base material which has been subjected to hydrochloric acid gas as an oil treatin medium.

6. An oil treating me ium comprising a base material and lithium chlorlde, said lithium chloride being held in suspende dispersion in saidbase material.

7. An oil treating medium com rising a porous base material having a sorptive properties and lithium chloride held in suspension in said base material.

8. An oil treating medium comprising lithium chloride and hydrous silicic acid mechanically combined in colloidal and molecular dispersion jelly.

In testimony whereof, we have afiixed our signatures.

. HERMAN REINBOLD.

HUGO REINBOLD.

in the form of a solid 

